1. The Field of the Invention
The present invention relates generally to flake-based pigments. More specifically, the present invention relates to composite reflective flake based pigments having improved specular reflectance.
2. The Relevant Technology
Pigments are generally used to contribute to the optical and other properties of coatings, inks, extrusions, paints, finishes, glass, ceramics, cosmetics, and the like. Many varieties of pigments exist, some of which are metal flake based. These metal flakes comprise a thin film metal layer for improving the lustre, sparkle, shine, absorption, hiding and/or reflective properties of the application. The optical performance of the pigments, however, is duly constrained by the inherent limitations of each metal flake therein.
In general, it is known that for the application to achieve the greatest specular reflectance across visible wavelengths (about 300-800 nm), metal flakes should individually lay as flat as possible. As a collection of numerous flakes, the greatest reflectance, and hence greatest brightness, occurs when the flakes are collectively planar oriented to expose the greatest amount of surface area of the metallic flakes to the incident light and reflect as much of that light as possible.
A major factor, however, affecting those reflectance characteristics is the size or dimensions of the flake as the flake is used in a particular application. For example, if the flakes are thick, a plurality of thick flakes combined together in an application are prevented from lying together in a generally flat or horizontal singular plane because adjacent flakes cannot easily overlap each other due to their thickness. As a result, many flakes are adversely caused to be oriented in a substantially vertical manner and the plurality of flakes do not lay with their area surfaces parallel to a common plane. Incident light then exposed upon the non-planar pigments is subject to extreme scatter and non-specular reflection. Thus, the favorable reflective properties of the application are diminished by thick flakes. To a lesser extent, thick flakes frequently cause other difficulties such as the clogging of automatic-spray paint guns during painting applications.
It is also well known that as the thicknesses of the flakes is reduced, the point is reached where the flakes become so flimsy (i.e., non-rigid or flaccid) that they begin to curl and or wrinkle. This reduction in flake planarity increases the scatter of incident light and reduces the desirable specular reflectivity. Additionally, if the flakes are too thin when applied onto a surface during applicational use, the flakes will assume any microscopic defects in the contour of that surface. For example, if that contour is rough, the flakes will correspondingly be rough or non-planar. As the flakes are distorted to conform with the surface, planarity is reduced, again increasing the scatter of incident light and reducing the desirable specular reflectivity. Some manufacturing processes form flakes from a singular, larger sheet or film of metal which is xe2x80x9cfracturedxe2x80x9d by well known techniques into smaller, flake-sized particles.
Two types of fracture may result, xe2x80x9cductilexe2x80x9d or xe2x80x9cbrittle.xe2x80x9d Ductile fractures cause the metal to undergo substantial plastic deformation near the vicinity of fracture before fracture occurs. This deformation causes numerous malformed regions having disfavorable planar characteristics to appear. As before, these malformed regions, such as regions having curled or wrinkled metal, disadvantageously tend to scatter and diffuse incident light exposed thereupon. Brittle fractures, on the other hand, tend to cause little or no plastic deformation of the metal before the fracture occurs which enables the produced metal flake to maintain, as much as possible, the original planarity of the larger metal sheet. Consequently, it is desirable that brittle fracture occur during manufacturing. However, brittle fracture does not occur with most metals having high reflectivity.
In fact, brittle fracture is only likely to occur with materials having a large compressive strength as compared to its corresponding tensile strength. This is because the internal bond strength distributed throughout a material is composed of tensile and compressive components. The tensile strength compensates for forces out of the plane of the material and the compressive strength is related to forces in the plane. Thus, similar compressive and tensile strengths will allow ductile deformations since the relative strength into and out of the plane is equivalent. In contrast, brittle deformation occurs when the compressive strength is greater than the tensile strength and the material strength is directed into the plane, not out of the plane. Consequently, a high compressive strength relative to tensile strength results in bond rupture and material cracking when a force is applied. Thus, aluminum, for example, which has a tensile strength of about 13-24 lb/in2 and a compressive strength of about 13-24 lb/in, would most likely undergo a ductile fracture under a uniaxial stress which would cause the aluminum to exhibit disfavored reflective characteristics. Moreover, once the aluminum is bent or deformed, as would occur with ductile fracture, the aluminum remains deformed and the disfavored reflective characteristics would persist. Consequently, it is difficult to manufacture metal flakes, such as aluminum, without malformations that reduce reflectance.
As is well known, fracture mechanics are not only important for metal flakes during the manufacturing process, but are as equally important during use. For example, applicational processes, such as the drying of a paint or ink solvent, also induce stresses on the flake. These stresses, caused by surface tension, again cause the flake to undergo fracture or malformation. Since brittle fracture of the flake during the applicational process also tends to produce smaller flakes that maintain much of the original planarity of the larger flake, instead of curled or deformed flakes, flake planarity and reflective properties are improved. Thus, flake brittleness is a characteristic not only preferred during the manufacturing process but also preferred during the applicational use.
Prior techniques have attempted to produce thin, rigid and brittle flakes by facilitating both the manufacturing thereof and the reflective properties of the application. Yet all prior solutions have involved compromises. For example, in U.S. Pat. No. 5,198,042, it is taught to alloy the metal flake with other materials and metals to reduce the adverse curling, wrinkling and malleability of thin flakes. Alloying, however, dilutes the reflectance properties of the flake. In U.S. Pat. No. 4,213,886, a surface bound species that pulls the flake flat in a coating resin is disclosed. This method, however, requires chemical tailoring of the flake and the resin in order achieve chemical compatibility with the species. Such compatibility is difficult and has not proved to be practical.
In U.S. Pat. No. 4,629,512, flakes are floated on a resin coating. Adversely, this method submits the flake to durability attacks because the flake is unprotected. Such attacks primarily include corrosion which not only corrodes the flake but tends to give the application a mottled or discolored appearance. Additionally, if this method were used in conjunction with another resinous application, such as a clear overcoat paint, the overcoat itself would tend to disfavorably disrupt the planar orientation of the flake because of solvent penetration. Again, reflectance properties would be decreased.
In U.S. Pat. No. 5,593,773, pre-cracked flakes are disclosed having such a small aspect ratio that malformation of the flake is essentially impossible. A shrinking aspect ratio, however, also correspondingly shrinks the inherent reflectance capability of the flake. This is because, as the aspect ratio becomes smaller, there is more opportunity for flakes to become disoriented with respect to flakes having their planes aligned parallel with the substrate surface.
In U.S. Pat. No. 3,622,473, flake rigidity is increased by oxidizing the reflector of the flake to form a rigid, outer oxide layer. Whenever an oxide is used, however, the inherent reflectance properties of the flake are decreased. Additionally, oxides are typically formed at defect sites on the flakes which then tend to prevent a uniform application across the surface of the flake. This non-uniformity introduces a reduction in reflectance and can also cause a mottled applicational appearance.
Various attempts have been made to improve flake rigidity by applying singular or multiple layer coatings about the surfaces thereof. Thus far, the singular layer coatings have been so thick that reflective properties are detrimentally diminished because the coatings have greatly contributed to the scatter of light. The multiple layer coatings have induced even more scatter and adversely caused light to diffuse at the boundaries between various layers.
In addition, prior coatings have commonly been organic, which inherently have a low elastic modulus, placing a limitation on how thinly the coatings can be applied and still provide structural rigidity to a very thin metal flake. Disadvantageously, the natural thickness limitation is still so large that other applicational processes remain burdened by this thickness. Such processes include spraying the flakes through an automatic-spray paint gun. Moreover, organic coatings when applicationally used in a solvent are eventually caused to lose structural rigidity because of dissolution related effects.
More recently, Japanese published application No. 10-259316 disclosed a method of preparing highly reflective pigments by sputtering metallic thin films on the surfaces of glass flakes. The glass flakes have an average particle diameter of 10-300 microns and an average thickness of 1-20 microns, with a 50-200 angstrom titanium metal film formed thereon by a sputtering process. In Japanese published application No. 10-316883, a method of preparing highly reflective pigments is disclosed in which metallic thin films of iron or nickel alloys are sputtered onto inorganic flakes such as glass, mica, aluminum, or graphite flakes.
Although some reflective coatings exist that are rigid and facilitate brittle fracture, these coatings are unlike most of the other prior coatings because they do not use a metal flake. In U.S. Pat. No. 4,309,075, for example, multiple layer coatings are taught that merely simulate a metal flake, with alternating layers of high and low indices of refraction used to create a reflector that simulates the reflective properties of a metal flake. Another example is described in U.S. Pat. No. 3,123,490, in which a layer of ZnS is coated on a top and bottom thereof with MgF2. Although rigid and subject to brittle fracture, this structure is typically thick (about 215 nm) and cannot be used in many applications requiring thin flakes. Moreover, it is often necessary to have numerous layers of alternating high-low refractive index coatings to achieve simulation of the metal flake. But as thicknesses and layers increase, manufacturing complexities and economic burdens correspondingly increase.
Accordingly, it is desirous to find alternatives for inexpensively producing a thin, rigid and brittle metal flake having improved reflective characteristics thereby improving reflectance of metal flake-based pigments.
It is an object of the present invention to provide an improved flake-based pigment containing substantially rigid thin flakes with good specular reflectance characteristics in the visible wavelength range.
It is a further object of the present invention to provide an improved flake-based pigment having thin flakes therein possessing brittle fracture properties to thereby afford improved reflectance characteristics during use.
It is another object of the present invention to provide a relatively cost-effective process of producing an improved flake-based pigment having thin, rigid and brittle flakes therein.
It is still another object of the present invention to provide an improved flake-based pigment containing flakes with a large aspect ratio.
It is yet another object of the present invention to provide an improved flake-based pigment wherein a metallic reflector of the flake is surrounded by a chemically resistant coating layer.
It is a further object of the present invention to provide flake-based pigments which may be easily and economically utilized in colorants such as paints and inks for various applications.
In accordance with the invention as embodied and broadly described herein, the foregoing and other objects are achieved by providing a flake-based pigment having a plurality of composite reflective flakes each formed of a central support layer and at least one reflector layer on either or both of the opposing major surfaces of the central support layer. The central support layer can be a dielectric material which provides a smooth, rigid support for the reflective layers. The composite reflective flakes are very thin structures that exhibit a uniaxial compressive strength much greater than a corresponding uniaxial tensile strength. This structure provides the benefits of rigidity and brittle fracture during manufacturing and application processes, which ultimately provides favorable planar and specular reflectance characteristics to the pigment in the visible wavelength range. The favorable properties of rigidity and brittleness allow easy fracture of a formed core flake film into small core flake sections during the manufacturing process without the flakes becoming curled or wrinkled. The composite reflective flakes also have a large aspect ratio, allowing for favorable reflection of substantial amounts of incident light during applicational use.
One or more coating layers can be formed around the fabricated composite reflective flakes according to various embodiments of the invention. Such coating layers can provide various desired optical characteristics to the pigment, such as color shift, color enhancement, magnetic properties, solar absorption properties, etc. Such coatings may also provide enhanced chemical resistance and durability, protecting the underlying metal layers responsible for the high specular reflectivity.
In a method of fabricating a highly reflective flake-based pigment according to the present invention, a first reflective layer is formed on an upper surface of a web material, and a dielectric central support layer is formed on the first reflective layer. A second reflective layer is then formed on the dielectric central support layer to complete a core flake film. The core flake film is then removed from the web material in order to produce a plurality of composite reflective flakes having substantial rigidity so as to provide high reflectance to the pigment. One or more coating layers are then formed around the composite reflective flakes as desired.
In an alternative method of fabricating a highly reflective flake-based pigment according to the present invention, first and second reflective layers are simultaneously deposited on the first and second major surfaces of preformed rigid flakes forming a composite reflective flake. One or more coating layers are then formed around the composite reflective flake as desired.
Other aspects and features of the present invention will become more fully apparent from the following description and appended claims, or may be learned by the practice of the invention.